Carboxylic acylating agents substituted with olefin polymers of high molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same

ABSTRACT

Hydrocarbyl substituted carboxylic acylating agents are made by reacting, optionally in the presence of chlorine or bromine, (A) one or more alpha-beta olefinically unsaturated carboxylic acid reagents containing 2 to about 20 carbon atoms, exclusive of the carboxyl-based groups with (B) one or more high molecular weight olefin polymers of more than 30 carbon atoms selected from the group consisting of 
     (i) polymers of C 12  -C 30  mono-olefins, and 
     (ii) chlorinated or brominated analogs of (i). 
     This invention includes the acylated amine and/or alcohol derivatives of these hydrocarbyl-substituted carboxylic acid acylating agents, and the use of such derivatives and agents in lubricants and normally liquid fuels.

FIELD OF THE INVENTION

This invention relates to olefin polymer substituted carboxylicacylating agents, and to derivatives thereof. This invention alsorelates to concentrates, and lubricant and normally liquid fuelcompositions containing such agents and derivatives, and to processesfor preparing such agents and derivatives.

BACKGROUND OF THE INVENTION

Hydrocarbyl-substituted carboxylic acylating agents having at least 30aliphatic carbon atoms in the substituent are known. The use of suchcarboxylic acylating agents as additives in normally liquid fuels andlubricants is discussed in U.S. Pat. Nos. 3,288,714 and 3,346,354. Theseacylating agents are also useful as intermediates for preparingadditives for use in normally liquid fuels and lubricants as describedin U.S. Pat. Nos. 2,892,786; 3,087,936; 3,163,603; 3,172,892; 3,189,544;3,215,707; 3,219,666; 3,231,587; 3,235,503; 3,272,746; 3,306,907;3,306,908; 3,331,776; 3,341,542; 3,346,354; 3,374,174; 3,379,515;3,381,022; 3,413,104; 3,450,715; 3,454,607; 3,455,728; 3,476,686;3,513,095; 3,523,768; 3,630,904; 3,632,511; 3,697,428; 3,755,169;3,804,763; 3,836,470; 3,862,981; 3,936,480; 3,948,909; 3,950,341 andFrench Pat. No. 2,223,415.

The preparation of such substituted carboxylic acid acylating agents isknown. Typically, such acylating agents are prepared by reacting one ormore olefin polymers which contain an average of, for example, fromabout 30 to about 300 aliphatic carbon atoms, with one or moreunsaturated carboxylic acid acylating agents.

The use of chlorine in the preparation of such acylating agents has beensuggested as a means for improving the conversion of the reaction ofolefin polymers and unsaturated carboxylic acid acylating agents.Methods for preparing substituted carboxylic acid acylating agents bythis method are disclosed in U.S. Pat. Nos. 3,215,707; 3,219,666;3,231,587; 3,787,374 and 3,912,764.

It would be advantageous to provide a hydrocarbyl substituted carboxylicacylating agent that could provide improved additive properties forlubricant and normally liquid fuel compositions. It would beadvantageous if such an acylating agent could also be useful as anintermediate for producing improved additives for use in such lubricantsand normally liquid fuels.

SUMMARY OF THE INVENTION

Hydrocarbyl substituted carboxylic acylating agents are provided inaccordance with the present invention which are useful in providingimproved additive properties for lubricants and normally liquid fuels.These acylating agents are also useful as intermediates for producingimproved lubricant and normally liquid fuel additives such asdetergents/dispersants and low temperature viscosity improvers.

Broadly stated, the present invention contemplates the provision of ahydrocarbyl-substituted carboxylic acylating agent made by reacting (A)one or more alpha-beta olefinically unsaturated carboxylic reagentscontaining two to about 20 carbon atoms exclusive of the carboxyl-basedgroups with (B) one or more olefin polymers of at least 30 carbon atomsselected from the group consisting of

(i) polymers of C₁₂ -C₃₀ mono-olefins, and

(ii) chlorinated or brominated analogs of (i).

The reaction between components (A) and (B) can optionally be conductedin the presence of chlorine or bromine. The present invention furtherprovides for compositions made by reacting the acylating agents of thepresent invention with one or more amines, one or more alcohols, ormixtures of said one or more amines and/or one or more alcohols. Thepresent invention also provides for concentrates containing suchacylating agents or compositions, and lubricant and normally liquid fuelcompositions containing such acylating agents or compositions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "hydrocarbyl" (and cognate terms such as hydrocarbyloxy,hydrocarbylmercapto, etc.) is used herein to include substantiallyhydrocarbyl groups (for example, substantially hydrocarbyloxy,substantially hydrocarbylmercapto, etc.), as well as purely hydrocarbylgroups. The description of these groups as being substantiallyhydrocarbyl means that they contain no non-hydrocarbyl substituents ornon-carbon atoms which significantly affect the hydrocarbylcharacteristics or properties of such groups relevant to their uses asdescribed herein. For example, in the context of this invention, apurely hydrocarbyl C₄₀ alkyl group and a C₄₀ alkyl group substitutedwith a methoxy substituent are substantially similar in their propertieswith regard to their use in this invention and would be hydrocarbyl.

Non-limiting examples of substituents which do not significantly alterthe hydrocarbyl characteristics or properties of the general nature ofthe hydrocarbyl groups of this invention are the following:

Ether groups (especially hydrocarbyloxy such as phenoxy, benzyloxy,methoxy, n-butoxy, etc., and particularly alkoxy groups of up to tencarbon atoms)

Oxo groups (e.g., --O-- linkages in the main carbon chain)

Nitro groups

Thioether groups (especially C₁₋₁₀ alkyl thioether)

Thia groups (e.g., --S-- linkages in the main carbon chain)

Carbohydrocarbyloxy groups (e.g., ##STR1## Sulfonyl groups (e.g.,##STR2## Sulfinyl groups (e.g., ##STR3## This list is intended to bemerely illustrative and not exhaustive, and the omission of a certainclass of substituent is not meant to require its exclusion. In general,if such substituents are present, there will not be more than two foreach ten carbon atoms in the substantially hydrocarbyl groups andpreferably not more than one for each ten carbon atoms since this numberof substituents usually will not substantially affect the hydrocarbylcharacteristics and properties of the group. Nevertheless, thehydrocarbyl groups usually will be free from non-hydrocarbon groups dueto economic considerations; that is, they will be purely hydrocarbylgroups consisting of only carbon and hydrogen atoms.

The term "lower" as used in the present specification and claims, whenused in conjunction with terms such as alkyl, alkenyl, alkoxy, and thelike, is intended to describe such radicals which contain a total of upto seven carbon atoms.

The Hydrocarbyl-Substituted Carboxylic Acylating Agents

The hydrocarbyl-substituted carboxylic acylating agents of the presentinvention are olefin polymer substituted carboxylic acid acylatingagents made by reacting (A) one or more alpha-beta olefinicallyunsaturated carboxylic acid reagents containing two to about 20 carbonatoms, exclusive of the carboxyl-based groups, with (B) one or moreolefin polymers containing at least 30 carbon atoms.

The alpha-beta olefinically unsaturated carboxylic acid reagents (A) maybe either the acid per se or functional derivatives thereof, e.g.,anhydrides, esters, acylated nitrogen, acyl halide, nitriles, metalsalts. These carboxylic acid reagents may be either monobasic orpolybasic in nature. When they are polybasic they are preferablydicarboxylic acids, although tri- and tetracarboxylic acids can be used.Exemplary of the monobasic alpha-beta olefinically unsaturatedcarboxylic acid reagents are the carboxylic acids corresponding to theformula: ##STR4## wherein R is hydrogen, or a saturated aliphatic oralicyclic, aryl, alkylaryl or heterocyclic group, preferably hydrogen ora lower alkyl group, and R₁ is hydrogen or a lower alkyl group. Thetotal number of carbon atoms in R and R₁ should not exceed 18 carbonatoms. Specific examples of useful monobasic alpha-beta olefinicallyunsaturated carboxylic acids are acrylic acid, methacrylic acid,cinnamic acid, crotonic acid, 3-phenyl propenoic acid,alpha,beta-decenoic acid, etc. Exemplary polybasic acids include maleicacid, fumaric acid, mesaconic acid, itaconic acid and citraconic acid.

The alpha-beta olefinically unsaturated reagents (A) can also befunctional derivatives of the foregoing acids. These functionalderivatives include the anhydrides, esters, acylated nitrogen, acidhalides, nitriles and metal salts of the afore-described acids. Apreferred alpha-beta olefinically unsaturated carboxylic acid reagent(A) is maleic anhydride. Methods of preparing such functionalderivatives are well known to those of ordinary skill in the art andthey can be satisfactorily described by noting the reactants used toproduce them. Thus, for example, derivative esters for use in thepresent invention can be made by esterifying monohydric or polyhydricalcohols or epoxides with any of the aforedescribed acids. Amines andalcohols described hereinafter can be used to prepare these functionalderivatives. The nitrile functional derivatives of the afore-describedcarboxylic acid useful in making the products of the present inventioncan be made by the conversion of a carboxylic acid to the correspondingnitrile by dehydration of the corresponding amide. The preparation ofthe latter is well known to those skilled in the art and is described indetail in The Chemistry of the Cyano Group edited by Zvi Rappoport,Chapter 2, which is hereby incorporated by reference for its relevantdisclosures pertaining to methods for preparing nitriles.

Ammonium salt acylated nitrogen functional derivatives can also be madefrom any of the amines described hereinafter as well as from tertiaryamino analogs of them (i.e., analogs wherein the --NH groups have beenreplaced with --N-hydrocarbyl or --N-hydroxy hydrocarbyl groups),ammonia or ammonium compounds (e.g., NH₄ Cl, NH₄ OH, etc) byconventional techniques well known to those of ordinary skill in theart.

The metal salt functional derivatives of the foregoing carboxylic acidreagents (A) can also be made by conventional techniques well known tothose of ordinary skill in the art. Preferably they are made from ametal, mixture of metals, or a basically reacting metal derivative suchas a metal salt or mixture of metal salts where the metal is chosen fromGroup Ia, Ib, IIa or IIb of the periodic table although metals fromGroups IVa, IVb, Va, Vb, VIa, VIb, VIIb and VIII can also be used. Thegegen ion (i.e., counter) of the metal salt can be inorganic such ashalide, sulfide, oxide, carbonate, hydroxide, nitrate, sulfate,thiosulfate, phosphite, phosphate, etc., or organic such as loweralkanoic, sulfonate, alcoholate, etc. The salts formed from these metalsand the acid products can be "acidic," "normal" or "basic" salts. An"acidic" salt is one in which the equivalents of acid exceed thestoichiometric amounts required to neutralize the number of equivalentsof metal. A "normal" salt is one wherein the metal and acid are presentin stoichiometrically equivalent amounts. A "basic" salt (sometimesreferred to as "overbased," "superbased" or "hyperbased" salts) is onewherein the metal is present in a stoichiometric excess relative to thenumber of stoichiometric equivalents of carboxylic acid compounds fromwhich it is produced. The production of the latter are well known tothose of ordinary skill in the art and are described in detail in"Lubricant Additives" by M. W. Ranney, pages 67-77, which is herebyincorporated by reference for its relevant disclosures pertaining tomethods for preparing overbased salts.

The acid halide functional derivative of the afore-described olefiniccarboxylic acids (A) can be prepared by the reaction of the acids andtheir anhydrides with a halogenation agent such as phosphorustribromide, phosphorus pentachloride, or thionyl chloride. Esters can beprepared by the reaction of the acid halide with the aforesaid alcoholsor phenolic compounds such as phenol, naphthol, octyl phenol, etc. Also,amides and imides and other acylated nitrogen derivatives can beprepared by reacting the acid halide with the above-described aminocompounds. These esters and acylated nitrogen derivatives can beprepared from the acid halides by conventional techniques well known tothose of ordinary skill in the art.

The olefin polymers (B) are selected from the group consisting of

(i) polymers of C₁₂ -C₃₀ mono-olefins, and

(ii) chlorinated or brominated analogs of (i).

These olefin polymers are preferably homopolymers and/or interpolymersof C₁₂ -C₃₀ mono-olefins and are aliphatic in nature. The description ofthese olefin polymers as being aliphatic is intended to denote that, ofthe total number of carbon atoms in the polymer, no more than about 20%are non-aliphatic carbon atoms; that is, carbon atoms which are part ofan alicyclic or aromatic ring. Thus, a polymer containing, e.g., 5% ofits carbon atoms in alicyclic ring structures and 95% of its carbon atomin aliphatic structures would be an aliphatic polymer within the contextof this invention.

The C₁₂₋₃₀ mono-olefins useful in preparing the olefin polymers (B) canbe internal olefins (i.e., when the olefinic unsaturation is not in the"-1-" or alpha position) or preferably 1-olefins. These C₁₂₋₃₀mono-olefins can be either straight or branched chain, but preferablythey are straight chain. Exemplary of such C₁₂₋₃₀ mono-olefins which canbe used to prepare the olefin polymers (B) of this invention are1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene,1-docosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-octacosene,1-nonacosene, etc. The preferred C₁₂₋₃₀ mono-olefins are thecommercially available alpha olefin fractions such as C₁₅₋₁₈alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins, C₁₄₋₁₈alpha-olefins, C₁₆₋₁₈ alpha-olefins, C₁₆₋₂₀ alpha-olefins, C₂₂₋₂₈alpha-olefins, etc.

Mono-olefins which are useful in the preparation of the olefin polymers(B) can be derived from the cracking of paraffin wax. The wax crackingprocess yields both even and odd number C₆₋₂₀ liquid olefins of which 85to 90 percent are straight chain 1-olefins. The balance of the crackedwax olefins is made up of internal olefins, branched olefins, diolefins,aromatics and impurities. Distillation of the C₆₋₂₀ liquid olefinsobtained from the wax cracking process yields fractions (i.e., C₁₅₋₁₈alpha-olefins) which are useful in preparing the olefin polymers of thisinvention.

Other mono-olefins which are useful in preparing the olefin polymers (B)can be derived from the ethylene chain growth process. This processyields even numbered straight chain 1-olefins from a controlled Zieglerpolymerization.

Other methods for preparing the mono-olefins of this invention includechlorination-dehydrochlorination of paraffin and catalyticdehydrogenation of paraffins.

The above procedures for the preparation of mono-olefins are well knownto those of ordinary skill in the art and are described in detail underthe heading "Olefins" in the Encyclopedia of Chemical Technology, SecondEdition, Kirk and Othmer, Supplement, Pages 632-657, IntersciencePublishers, Div. of John Wiley and Son, 1971, which is herebyincorporated by reference for its relevant disclosures pertaining tomethods for preparing mono-olefins.

As noted above, the olefin polymers (B) used in this invention cancontain small amounts of alicyclic carbon atoms. Such alicyclic carbonatoms can be derived from such monomers as cyclopentene, cyclohexene,ethylene cyclopentane, methylene cyclohexene, 1,3-cyclohexene,norbornene, norboradiene and cyclopentadiene.

The olefin polymers (B) used in this invention are also substantiallysaturated in nature. That is, their molecules contain no more than 10%olefinic or acetylenic unsaturation. In other words, there is no morethan one olefinic or acetylenic carbon-carbon bond for every tenmonovalent carbon-carbon bonds in the molecules of the polymers.Normally, the polymers are free from acetylenic unsaturation.

The olefin polymers (B) used in this invention contain at least about 30aliphatic carbon atoms; preferably, they contain an average of up toabout 3500 carbon atoms; preferably, they contain an average of about 50to about 700 carbon atoms. In terms of molecular weight, the polymers(B) used in this invention have number average molecular weights asdetermined by gel permeation chromatography of at least about 420, morepreferably, they have a maximum number average molecular weight asdetermined by gel permeation chromatography of no more than about50,000; an especially preferred range for number average molecularweights of the polymers (B) used in this invention is about 750 to about10,000. A particularly preferred range of number average molecularweights is from about 750 to about 3,000. The preferred weight averagemolecular weight as determined by gel permeation chromatography is atleast about 420 up to about 100,000, more preferably about 1,500 toabout 20,000.

The molecular weight of the polymers used in this invention can also bedefined in terms of inherent viscosity. The inherent viscosity (n_(inh))of these polymers generally is at least about 0.03, preferably at leastabout 0.07 and being no more than about 1.5, preferably no more than 0.2deciliters per gram. These inherent viscosities are determined atconcentrations of 0.5 gram of polymer in 100 ml. of carbon tetrachlorideand at 30° C.

The olefin polymers (B) of this invention are most conveniently obtainedby the polymerization of the olefins with Friedel-Crafts polymerizationcatalyst such as aluminum chloride, boron trifluoride, titaniumtetrachloride, or the like. The polymers could also be obtained by theuse of "Ziegler Type" catalysts. These catalysts generally include atransition metal compound such as the halide, oxide or alkoxide and anorgano-metallic compound wherein the metal is of the Group I--III of thePeriodic Chart. Generally, titanium tri- or tetrachloride or vanadiumtrichloride or oxychloride is combined witha trialkyl or dialkylaluminum halide such as triethyl aluminum, triisobutyl aluminum ordiethyl aluminum chloride.

Additionally, the olefin polymers (B) of this invention can be obtainedby chain polymerization of the olefins by the use of free-radicalinitiators. The free-radical initiators commonly used are organicperoxides. The preferred organic peroxides are di-t-butyl peroxide andbenzoyl peroxide. Chain polymerization is well known to those ofordinary skill in the art and is discussed more fully in Schildknecht,C. E., Allyl Compounds and Their Polymers, Wiley-Interscience, 1973, pp.62-63 which is incorporated by reference for its relevant disclosurepertaining to methods of chain polymerization and free-radicalinitiators useful in chain polymerization.

The hydrocarbyl substituted carboxylic acylating agents of the presentinvention can be prepared by directly contacting one or more alpha-betaolefinically unsaturated carboxylic reagents (A) with one or more olefinpolymers (B) at a temperature in the range of, for example, about 140°C. to about 300° C. The processes for preparing hydrocarbyl-substitutedcarboxylic acid acylating agents are well known to those of ordinaryskill in the art and have been described in detail, for example, in U.S.Pat. Nos. 3,087,936; 3,163,603; 3,172,892; 3,189,544; 3,219,666;3,231,587; 3,272,746; 3,288,714; 3,306,907; 3,331,776; 3,340,281;3,341,542; 3,346,354; and 3,381,022 which are incorporated herein byreference.

The hydrocarbyl-substituted carboxylic acylating agent compositions ofthis invention can also be prepared by reacting one or more alpha-betaolefinically unsaturated carboxylic reagents (A) with one or more olefinpolymers (B) in the presence of chlorine or bromine at a temperaturewithin the range of about 100° C. to about 300° C. according to thetechniques disclosed in U.S. Pat. Nos. 3,215,707, 3,231,587, and3,912,764, which are incorporated herein by reference.

The chlorinated or brominated analogs of the olefin polymer (B) can beprepared by conventional techniques well known to those of ordinaryskill in the art. For example, the chlorinated analogs of the olefinpolymers (B) can be prepared by contacting (i.e., reacting) a 1:1 moleratio of the olefin polymer (B) with chlorine at 100°-200° C. Excesschlorine may be used; for example, about 1.1 to about 3 moles ofchlorine for each mole of olefin polymer (B).

The olefin polymer (B) or chlorinated or brominated analog thereof isgenerally reacted at a ratio of one equivalent of olefin polymer (B) orchlorinated or brominated analog thereof (for purposes of this inventionthe equivalent weight of the olefin polymer (B) is equal to its numberaverage molecular weight, as determined by gel permeationchromatography) to from about 0.1 to about 5 moles, usually 0.1 to about1 mole, with the unsaturated carboxylic reagent (A).

When the olefin polymer (B) and the unsaturated carboxylic reagents (A)are reacted in the presence of chlorine or bromine, the ratios of thereactants are the same as hereinabove-described. The molar ratio ofunsaturated carboxylic reagent (A) to chlorine or bromine is generallyone mole of (A) to about 0.5 up to about 1.3 mole, usually from about 1up to about 1.05 mole, of chlorine or bromine.

Reaction Products of the Hydrocarbyl-Substituted Carboxylic AcylatingAgents with Amines and/or Alcohols

Also included in this invention are the compositions made by reactingthe hydrocarbyl-substituted carboxylic acylating agents of the presentinvention with one or more amines, or one or more alcohols, or mixturesof one or more amines and/or one or more alcohols.

The amines useful for reacting with the hydrocarbyl-substitutedcarboxylic acylating agents of this invention are characterized by thepresence within their structure of at least one H--N< group. Theseamines can be monoamines or polyamines. Hydrazine and substitutedhydrazines containing up to three substituents are included as aminessuitable for preparing carboxylic derivative compositions. Mixtures oftwo or more amines can be used in the reaction with one or more of theacylating agents of the present invention. Preferably, the aminecontains at least one primary amino group (i.e., --NH₂). Advantageously,the amine is a polyamine, especially a polyamine containing at least twoH--N< groups, either or both of which are primary or secondary amines.The use of polyamines result in carboxylic derivative compositions whichare usually more effective as dispersant/detergent additives, than arederivative compositions derived from monoamines. Suitable monoamines andpolyamines are described in greater detail hereinafter.

Alcohols which can be reacted with the hydrocarbyl-substitutedcarboxylic acylating agents of the present invention include monohydricand polyhydric alcohols. Polyhydric alcohols are preferred since theyusually result in carboxylic derivative compositions which are moreeffective as dispersant/detergents than carboxylic derivativecompositions derived from monohydric alcohols. Alcohols suitable for usein this invention are described in greater detail hereinafter.

The monoamines and polyamines useful in this invention are characterizedby the presence within their structure of at least one H--N< group.Therefore, they have at least one primary (i.e., H₂ N--) or secondaryamino (i.e., H--N═) group. The amines can be aliphatic, cycloaliphatic,aromatic, or heterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic,aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic-substituted aromatic,cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic,aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substitutedcycloaliphatic, and heterocyclic-substituted aromatic amines and may besaturated or unsaturated. If unsaturated, the amine is preferably freefrom acetylenic unsaturation (i.e., --C═C--). The amines may alsocontain non-hydrocarbon substituents or groups as long as these groupsdo not significantly interfere with the reaction of the amines with theacylating reagents of this invention. Such non-hydrocarbon substituentsor groups include lower alkoxy, lower alkyl mercapto, nitro,interrupting groups such as --O--and --S--(e.g., as in such groups as--CH₂ CH₂ --X--CH₂ CH₂ -- where X is --O-- or --S--).

With the exception of the branched polyalkylene polyamines, thepolyoxyalkylene polyamines and the high molecular weighthydrocarbyl-substituted amines described more fully hereafter, theamines used in this invention ordinarily contain less than about 40carbon atoms in total and usually not more than about 20 carbon atoms intotal.

Aliphatic monoamines include mono-aliphatic and di-aliphatic substitutedamines wherein the aliphatic groups can be saturated or unsaturated andstraight or branched chain. Thus, they are primary or secondaryaliphatic amines. Such amines include, for example, mono- anddi-alkyl-substituted amines, mono- and di-alkenyl-substituted amines,and amines having one N-alkenyl substituent and one N-alkyl substituentand the like. The total number of carbon atoms in these aliphaticmonoamines preferably do not exceed about 40 and usually do not exceedabout 20 carbon atoms. Specific examples of such monoamines includeethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine,isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine,oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and thelike. Examples of cycloaliphatic-substituted aliphatic amines,aromatic-substituted aliphatic amines, and heterocyclic-substitutedaliphatic amines, include 2-(cyclohexyl)-ethylamine, benzylamine,phenylethylamine, and 3-(furylpropyl)amine.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine,dicyclohexylamines, and the like. Examples of aliphatic-substituted,aromatic-substituted, and heterocyclic-substituted cycloaliphaticmonoamines include propyl-substituted cyclohexylamines,phenyl-substituted cyclopentylamines, and pyranyl-substitutedcyclohexylamine.

Suitable aromatic amines include those monoamines wherein a carbon atomof the aromatic ring structure is attached directly to the aminonitrogen. The aromatic ring will usually be a mononuclear aromatic ring(i.e., one derived from benzene) but can include fused aromatic rings,especially those derived from maphthylene. Examples of aromaticmonoamines include aniline, di(para-methylphenyl)amine, naphthylamine,N-(n-butyl)aniline, and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines are para-ethoxyaniline, para-dodecylaniline,cyclohexyl-substituted naphthylamine, and thienyl aniline.

Suitable polyamines are aliphatic, cycloaliphatic and aromaticpolyamines analogous to be above-described monoamines except for thepresence within their structure of another amino nitrogen. The otheramino nitrogen can be a primary, secondary or tertiary amino nitrogen.Examples of such polyamines include N-aminopropyl-cyclohexylamines,N-N'-di-n-butyl-para-phenylene diamine, bis-(para-aminophenyl)-methane,1,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be used in making thesubstituted carboxylic acid acylating agent derivative compositions ofthis invention. As used herein, the terminology "heterocyclic mono- andpolyamine(s)" is intended to describe those heterocyclic aminescontaining at least one primary or secondary amino group and at leastone nitrogen as a heteroatom in the heterocyclic ring. However, as longas there is present in the heterocyclic mono- and polyamines at leastone primary or secondary amino group, the hetero-N atom in the ring canbe a tertiary amino nitrogen; that is, one that does not have hydrogenattached directly to the ring nitrogen. Heterocyclic amines can besaturated or unsaturated and can contain various substituents such asnitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkylsubstituents. Generally, the total number of carbon atoms in thesubstituents will not exceed about 20. Heterocyclic amines can containheteroatoms other than nitrogen, especially oxygen and sulfur. Obviouslythey can contain more than one nitrogen heteroatom. The five- andsix-membered heterocyclic rings are preferred.

Among the suitable heterocyclics are aziridines, azetidines, azolidines,tetra- and di-hydro pyridines, pyrroles, indoles, piperadines,imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles,purines, morpholines, thiomorpholines, N-aminoalkylmorpholines,N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines, azecinesand tetra-, di- and perhydro-derivatives of each of the above andmixtues of two or more of these heterocyclic amines. Preferredheterocyclic amines are the saturated 5- and 6-membered heterocyclicamines containing only nitrogen, oxygen and/or sulfur in the heteroring, especially the piperidines, piperazines, thiomorpholines,morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substitutedpiperazines, morpholine, aminoalkyl-substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especiallypreferred. Usually the aminoalkyl substituents are substituted on anitrogen atom forming part of the hetero ring. Specific examples of suchheterocyclic amines include N-aminopropylmorpholine,N-aminoethylpiperazine, and N,N'-di-aminoethylpiperazine.

Hydroxyamines both mono- and polyamines, analogous to those describedabove are also useful in this invention provided they contain at leastone primary or secondary amino group. Hydroxy-substituted amines havingonly tertiary amino nitrogen such as in tri-hydroxyethyl amine, are thusexcluded as an amine, but can be used as an alcohol as disclosedhereafter. The hydroxy-substituted amines contemplated are those havinghydroxy substituents bonded directly to a carbon atom other than acarbonyl carbon atom; that is, they have hydroxy groups capable offunctioning as alcohols. Examples of such hydroxy-substituted aminesinclude ethanolamine, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine,4-hydroxybutylamine, diethanolamine, di-(2-hydroxypropyl)-amine,N-(hydroxypropyl)propylamine, pylamine,N-(2-hydroxyethyl)-cyclohexylamine, 3-hydroxycyclopentylamine,para-hydroxyaniline, N-hydroxyethyl piperazine, and the like.

The terms hydroxyamine and aminoalcohol describe the same class ofcompounds and, therefore, can be used interchangeably. Hereinafter, inthe specification and appended claims, the term hydroxyamine will beunderstood to include aminoalcohols as well as hydroxyamines.

Also suitable as amines are the aminosulfonic acids and derivativesthereof corresponding to the formula: ##STR5## wherein R is --OH, --NH₂,ONH₄, etc., R_(a) is a polyvalent organic radical having a valence equalto x+y; R_(b) and R_(c) are each independently hydrogen, hydrocarbyl,and substituted hydrocarbyl with the proviso that at least one of R_(b)and R_(c) is hydrogen per aminosulfonic acid molecule; x and y are eachintegers equal to or greater than one. From the formula, it is apparentthat each aminosulfonic reactant is characterized by at least one HN<orH₂ N- group and at least one ##STR6## group. These sulfonic acids can bealiphatic, cycloaliphatic, or aromatic aminosulfonic acids and thecorresponding functional derivatives of the sulfo group. Specifically,the aminosulfonic acids can be aromatic aminosulfonic acids, that is,where R_(a) is a polyvalent aromatic radical such as phenylene where atleast one ##STR7## group is attached to a nuclear carbon atom of thearomatic radical. The aminosulfonic acid may also be a mono-aminoaliphatic sulfonic acid; that is, an acid where x is one and R_(a) is apolyvalent aliphatic radical such as ethylene, propylene, trimethylene,and 2-methylene propylene. Other suitable aminosulfonic acids andderivatives thereof useful as amines in this invention are disclosed inU.S. Pat. Nos. 3,926,820; 3,029,250; and 3,367,864; which areincorporated herein by reference.

Hydrazine and substituted-hydrazine can also be used as amines in thisinvention. At least one of the nitrogens in the hydrazine must contain ahydrogen directly bonded thereto. Preferably there are at least twohydrogens bonded directly to hydrazine nitrogen and, more preferably,both hydrogens are on the same nitrogen. The substituents which may bepresent on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl,and the like. Usually, the substituents are alkyl, especially loweralkyl, phenyl, and substituted phenyl such as lower alkoxy-substitutedphenyl or lower alkyl-substituted phenyl. Specific examples ofsubstituted hydrazines are methylhydrazine, N,N-dimethylhydrazine,N,N'-dimethylhydrazine, phenyl-hydrazine, N-phenyl-N'-ethylhydrazine,N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine,N-(para-nitrophenyl)-N-methylhydrazine,N,N'-di-(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine,and the like.

The high molecular weight hydrocarbyl amines, both monoamines andpolyamines, which can be used as amines in this invention are generallyprepared by reacting a chlorinated polyolefin having a molecular weightof at least about 400 with ammonia or amine. Such amines are known inthe art and described, for example, in U.S. Pat. No. 3,275,554 and3,438,757, both of which are expressly incorporated herein by referencefor their disclosure in regard to how to prepare these amines. All thatis required for use of these amines is that they possess at least oneprimary or secondary amino group.

Another group of amines suitable for use in this invention are branchedpolyalkylene polyamines. The branched polyalkylene polyamines arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylene##STR8## group per nine amino units present on the main chain, forexample, 1-4 of such branched chains per nine units on the main chain,but preferably one side chain unit per nine main primary amino groupsand at least one tertiary amino group.

These reagents may be expressed by the formula: ##STR9## Wherein R is analkylene group such as ethylene, propylene, butylene and other homologs(both straight chained and branched), etc., but preferably ethylene; andx, y and z are integers, x being, for example, from 4 to 24 or more butpreferably 6 to 18, y being, for example, 1 to 6 or more but preferably1 to 3, and z being, for example, 0-6 but preferably 0-1. The x and yunits may be sequential, alternative, orderly or randomly distributed.

The preferred class of such polyamines includes those of the formula:##STR10## wherein n is an integer, for example, 1-20 or more butpreferably 1-3, and R is preferably ethylene, but may be propylene,butylene, etc. (straight chained or branched).

The preferred embodiments are presented by the following formula:##STR11##

The radicals in the brackets may be joined in a head-to-head or ahead-to-tail fashion. Compounds described by this formula wherein n=1-3are manufactured and sold as Polyamines N-400, N-800, N-1200, etc.Polyamine N-400 has the above formula wherein n=1.

U.S. Pat. Nos. 3,200,106 and 3,259,578 are incorporated herein byreference for their disclosure of how to make such polyamines andprocesses for reacting them with carboxylic acid acylating agents.

Suitable amines also include polyoxyalkylene polyamines, e.g.,poyloxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to 400 and preferably fromabout 400 to 2000. Illustrative examples of these polyoxyalkylenepolyamines may be characterized by the formulae:

    NH.sub.2 --Alkylene-- O-Alkylene  ).sub.m NH.sub.2

where m has a value of about 3 to 70 and preferably about 10 to 35; and

    R--[Alkylene-- O-Alkylene  ).sub.n NH.sub.2 ].sub.3-6

wherein n is such that the total value is from about 1 to 40 with theproviso that the sum of all of the n's is from about 3 to about 70 andgenerally from about 6 to about 35, and R is a polyvalent saturatedhydrocarbyl radical of up to ten carbon atoms having a valence of 3 to6. The alkylene groups may be straight or branched chains and containfrom 1 to 7 carbon atoms, and usually from 1 to 4 carbon atoms. Thevarious alkylene groups present within the above formulae may be thesame or different.

More specific examples of these polyamines include: ##STR12## wherein xhas a value of from about 3 to 70 and preferably from about 10 to 35and: ##STR13## wherein x+y+z have a total value ranging from about 3 to30 and preferably from about 5 to 10.

Preferred polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeff-amines D-230, D-400, D-1000, D-2000, T-403, etc.".

U.S. Pat. Nos. 3,804,763 and 3,948,800 are incorporated herein byreference for their disclosure of such polyoxyalkylene polyamines andprocess for acylating them with carboxylic acid acylating agents.

Preferred amines are the alkylene polyamines, including the polyalkylenepolyamines, as described in more detail hereafter. The alkylenepolyamines include those conforming to the formula: ##STR14## wherein nis from 1 to about 10; each R" is independently a hydrogen atom, ahydrocarbyl group or a hydroxy-substituted hydrocarbyl group having upto about 30 atoms, and the "Alkylene" group has from about 1 to about 10carbon atoms but the preferred alkylene is ethylene or propylene.Especially preferred are the alkylene polyamines where each R" ishydrogen with the ethylene polyamines and mixtures of ethylenepolyamines being the most preferred. Usually n will have an averagevalue of from about 2 to about 7. Such alkylene polyamines includemethylene polyamines, ethylene polyamines, butylene polyamines,propylene polyamines, pentylene polyamines, hexylene polyamines,heptylene polyamines, etc. The higher homologs of such amines andrelated aminoalkyl-substituted piperazines are also included.

Alkylene polyamines useful in preparing the carboxylic derivativecompositions include ethylene diamine, triethylene tetramine, propylenediamine, trimethylene diamine, hexamethylene diamine, decamethylenediamine, octamethylene diamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazne,1,4-bis(2-aminoethyl)piperazine, and the like. Higher homologs as areobtained by condensing two or more of the above-illustrated alkyleneamines are useful as amines in this invention as are mixtures of two ormore of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are especiallyuseful for reasons of cost and effectiveness. Such polyamines aredescribed in detail under the heading "Diamines and Higher Amines" inThe Encyclopedia of Chemical Technology, Second Edition, Kirk andOthmer, Volume 7, pages 27-39, Interscience Publishers, Division of JohnWiley and Sons. 1965, which is hereby incorporated by reference fortheir disclosure of useful polyamines. Such compounds are prepared mostconveniently by the reaction of an alkylene chloride with ammonia or byreaction of an ethylene imine with a ring-opening reagent such asammonia, etc. These reactions result in the production of the somewhatcomplex mixtures of alkylene polyamines, including cyclic condensationproducts such as piperazines.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstitutents on the nitrogen atoms, are also useful in preparingcompositions of the present invention. Preferredhydroxyalkyl-substituted alkylene polyamines are those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl)ethylene diamine,N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropyl-substituted etraethylene pentamine,N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as areobtained by condensation of the above-illustrated hydroxy alkylenepolyamines through amino radicals or through hydroxy radicals arelikewise useful as amines in this invention. Condensation through aminoradicals results in a higher amine accompanied by removal of ammonia andcondensation through the hydroxy radicals results in products containingether linkages accompanied by removal of water.

The carboxylic derivative compositions produced from the reaction of thehydrocarbyl-substituted carboxylic acylating agents of this inventionand the amines described hereinbefore yield acylated amines whichinclude amine salts, amides, imides and imidazolines as well as mixturesthereof. To prepare carboxylic derivatives from the acylating agents andamines, one or more acylating agents and one or more amines are heated,optionally in the presence of a normally liquid, substantially inertorganic liquid solvent/diluent, at temperatures in the range of about80° C. up to the decomposition point (the decomposition point is thetemperature at which there is sufficient decomposition of any reactantor product such as to interfere with the production to the desiredproduct) but normally at temperatures in the range of about 100° C. toabout 300° C., provided 300° C. does not exceed the decomposition point.Temperatures of about 125° C. to about 250° C. are normally used. Theacylating agent and the amine are reacted in amounts sufficient toprovide from about one-half equivalent to about 2 moles of amine perequivalent of acylating agent. For purposes of this invention anequivalent of amine is that amount of the amine corresponding to thetotal weight of amine divided by the total number of nitrogens present.Thus, octylamine has an equivalent weight equal to its molecular weight;ethylene diamine has an equivalent weight equal to one-half itsmolecular weight; and aminoethylpiperazine has an equivalent weightequal to one-third its molecular weight. Also, for example, theequivalent weight of a commercially available mixture of polyalkylenepolyamine can be determined by dividing the atomic weight of nitrogen(14) by the %N contained in the polyamine. Therefore, a polyaminemixture having a %N of 34 would have an equivalent weight of 41.2. Thenumber of equivalents of acylating agent depends on the number ofcarboxylic functions (e.g., carboxylic acid groups or functionalderivatives thereof) present in the acylating agent. Thus, the number ofequivalents of acylating agents will vary with the number of carboxygroups present therein. In determining the number of equivalents ofacylating agents, those carboxyl functions which are not capable ofreacting as a carboxylic acid acylating agent are excluded. In general,however, there is one equivalent of acylating agent for each carboxygroup in the acylating agents. For example, there would be twoequivalents in the acylating agents derived from the reaction of onemole of olefin polymer and one mole of maleic anhydride. Conventionaltechniques are readily available for determining the number of carboxylfunctions (e.g., acid number, saponification number) and, thus, thenumber of equivalents of acylating agent available to react with amine.

Because the acylating agents of this invention can be used in the samemanner as the high molecular weight acylating agents of the prior art inpreparing acylated amines suitable as additives for lubricating oilcompositions, U.S. Pat. Nos. 3,172,892; 3,219,666; and 3,272,746 areincorporated herein by reference for their disclosures with respect tothe procedures applicable to reacting the substituted carboxylic acidacylating agents of this invention with the amines as described above.In applying the disclosures of these patents to thehydrocarbyl-substituted carboxylic acylating agents of this invention,the latter can be substituted for the high molecular weight carboxylicacid acylating agents disclosed in these patents on an equivalent basis.That is, where one equivalent of the high molecular weight carboxylicacylating agent disclosed in these incorporated patents is utilized, oneequivalent of the acylating agent of this invention can be used. Thesepatents are also incorporated by reference for their disclosure of howto use the acylated amines thus produced as additives in lubricating oilcompositions. Dispersant/detergent properties can be imparted tolubricating oils by incorporating the acylated amines produced byreacting the acylating agents of this invention with the aminesdescribed above on an equal weight basis with the acylated aminesdisclosed in these patents.

Alcohols useful in preparing carboxylic derivative compositions of thisinvention from the acylating agents previously described include thosecompounds of the general formula:

    R.sub.1 --(OH).sub.m

wherein R₁ is a monovalent or polyvalent organic radical joined to the--OH groups through carbon-to-oxygen bonds (that is, --COH wherein thecarbon is not part of a carbonyl group) and m is an integer of from 1 toabout 10, preferably 2 to about 6. As with the amine reactants, thealcohols can be aliphatic, cycloaliphatic, aromatic, and heterocyclic,including aliphatic-substituted cycloaliphatic alcohols,aliphatic-substituted aromatic alcohols, aliphatic-substitutedheterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substitutedheterocyclic alcohols, heterocyclic-substituted aliphatic alcohols,heterocyclic-substituted cycloaliphatic alcohols, andheterocyclic-substituted aromatic alcohols. Except for thepolyoxyalkylene alcohols, the mono- and polyhydric alcoholscorresponding to the formula R₁ --(OH)_(m) will usually contain not morethan about 40 carbon atoms and generally not more than about 20 carbonatoms. The alcohols may contain non-hydrocarbon substituents of the sametype mentioned with respect to the amines above, that is,non-hydrocarbon substituents which do not interfere with the reaction ofthe alcohols with the acylating reagents of this invention. In general,polyhydric alcohols are preferred.

Among the polyoxyalkylene alcohols suitable for use in the preparationof the carboxylic derivative compositions of this invention are thepolyoxyalkylene alcohol demulsifiers for aqueous emulsions. Theterminology "demulsifier for aqueous emulsions" as used herein isintended to describe those polyoxyalkylene alcohols which are capable ofpreventing or retarding the formation of aqueous emulsions or "breaking"aqueous emulsions. The terminology "aqueous emulsion" is generic tooil-in-water and water-in-oil emulsions.

Many commercially available polyoxyalkylene alcohol demulsifiers can beused. Useful demulsifiers are the reaction products of various organicamines, carboxylic acid amides, and quaternary ammonium salts withethylene-oxide. Such polyoxyethylated amines, amides, and quaternarysalts are available from Armour Industrial Chemical Co. under the namesEthoduomeen T, an ethyleneoxide condensation product of an N-alkylalkylenediamine under the name Duomeen T; Ethomeens, tertiary amineswhich are ethyleneoxide condensation products of primary fatty amines;Ethomids, ethyleneoxide condensates of fatty acid amides; and Ethoquads,polyoxyethylated quaternary ammonium salts such as quaternary ammoniumchlorides.

Preferred demulsifiers are liquid polyoxyalkylene alcohols andderivatives thereof. The derivatives contemplated are the hydrocarbylethers and the carboxylic acid esters obtained by reacting the alcoholswith various carboxylic acids. Illustrative hydrocarbyl groups arealkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc., containingup to about forty carbon atoms. Specific hydrocarbyl groups are methyl,butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenylethyl, cyclohexyl, and the like. Carboxylic acids useful in preparingthe ester derivatives are mono- or polycarboxylic acids such as aceticacid, valeric acid, lauric acid, stearic acid, succinic acid, and alkylor alkenyl-substituted succinic acids wherein the alkyl or alkenyl groupcontains up to about twenty carbon atoms. Members of this class ofalcohols are commercially available from various sources; e.g., Pluronicpolyols from Wyandotte Chemicals Corporation; Polyglycol 112-2, a liquidtriol derived from ethyleneoxide and propyleneoxide available from DowChemical Co.; and Tergitols, dodecylphenyl or nonylphenyl polyethyleneglycol ethers, and Ucons, polyalkylene glycols and various derivativesthereof, both available from Union Carbide Corporation. However, thedemulsifiers used must have an average of at least one free alcoholichydroxyl group per molecule of polyoxyalkylene alcohol. For purposes ofdescribing these polyoxyalkylene alcohols which are demulsifiers, analcoholic hydroxyl group is one attached to a carbon atom that does notform part of an aromatic nucleus.

In this class of preferred polyoxyalkylene alcohols are those polyolsprepared as "block" copolymers. Thus, a hydroxy-substituted compound, R₂--(OH)_(q) (where q is 1 to 6, preferably 2 to 3, and R₂ is the residueof a mono- or polyhydric alcohol or mono- or polyhydroxy phenol,naphthol, etc.) is reacted with an alkylene oxide, ##STR15## to form ahydrophobic base, R₃ being a lower alkyl group of up to four carbonatoms, R₄ being H or the same as R₃ with the proviso that the alkyleneoxide does not contain in excess of ten carbon atoms. This base is thenreacted with ethylene oxide to provide a hydrophilic portion resultingin a molecule having both hydrophobic and hydrophilic portions. Therelative sizes of these portions can be adjusted by regulating the ratioof reactants, time of reaction, etc., as is obvious to those skilled inthe art. It is within the skill of the art to prepare such polyols whosemolecules are characterized by hydrophobic and hydrophilic moietiespresent in a ratio rendering them suitable as demulsifiers for aqueousemulsions in various lubricant compositions and thus suitable asalcohols in the invention. Thus, if more oil-solubility is needed in agiven lubricant composition, the hydrophobic portion can be increasedand/or hydrophilic portion decreased. If greater aqueous emulsionbreaking capability is required, the hydrophilic and/or hydrophobicportions can be adjusted to accomplish this.

Compounds illustrative of R₁ --(OH)_(q) include aliphatic polyols suchas the alkylene glycols and alkane polyols, e.g., ethylene glycol,propylene glycol, trimethylene glycol, glycerol, pentaerythritol,erythritol, sorbitol, mannitol, and the like and aromatic hydroxycompounds such as alkylated mono- and polyhydric phenols and naphthols,e.g., cresols, heptylphenols, dodecylphenols, dioctylphenols,triheptylphenols, resorcinol, pyrogallol, etc.

Polyoxyalkylene polyol demulsifiers which have two or three hydroxylgroups and molecules consisting essentially of hydrophobic portionscomprising ##STR16## where R₁ is lower alkyl of up to three carbon atomsand hydrophilic portions comprising --CH₂ CH₂ O-- groups areparticularly preferred. Such polyols can be prepared by first reacting acompound of the formula R₁ --(OH)_(q) where q is 2-3 with a terminalalkylene oxide of the formula ##STR17## and then reacting that productwith ethylene oxide. R₁ --(OH)_(q) can be, for example, TMP(trimethylolpropane), TME (trimethylolethane), ethylene glycol,trimethylene glycol, tetramethylene glycol,tri-(beta-hydroxypropyl)amine, 1,4-(2-hydroxyethyl)-cyclohexane,N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine,N,N,N',N'-tetrakis(2-hydroxyethyl)ethylene diamine, naphthol, alkylatednaphthol, resorcinol, or one of the other illustrative examplesmentioned hereinbefore.

The polyoxyalkylene alcohol demulsifiers should have an averagemolecular weight of 1000 to about 10,000, preferably about 2000 to about7000. The ethyleneoxy groups (i.e., --CH₂ CH₂ O--) normally willcomprise from about 5% to about 40% of the total average molecularweight. Those polyoxyalkylene polyols where he ethyleneoxy groupscomprise from about 10% to about 30% of the total average molecularweight are especially useful. Polyoxyalkylene polyols having an averagemolecular weight of about 2500 to about 6000 where approximately 10%-20%by weight of the molecule is attributable to ethyleneoxy groups resultin the formation of esters having particularly improved demulsifyingproperties. The ester and ether derivatives of these polyols are alsouseful.

Representative of such polyoxyalkylene polyols are the liquid polyolsavailable from Wyandotte Chemicals Company under the name PluronicPolyols and other similar polyols. These Pluronic Polyols correspond tothe formula ##STR18## wherein x, y, and z are integers greater than 1such that the --CH₂ CH₂ O-- groups comprise from about 10% to about 15%by weight of the total molecular weight of the glycol, the averagemolecular weight of said polyols being from about 2500 to about 4500.This type of polyol can be prepared by reacting propylene glycol withpropylene oxide and then with ethylene oxide.

Another group of polyoxyalkylene alcohol demulsifiers illustrative ofthe preferred class discussed above are the commercially availableliquid Tetronic polyols sold by Wyandotte Chemicals Corporation. Thesepolyols are represented by the general formula: ##STR19## Such polyolsare described in U.S. Pat. No. 2,979,528 which is incorporated herein byreference. Those polyols corresponding to the above formula having anaverage molecular weight of up to about 10,000 wherein the ethyleneoxygroups contribute to the total molecular weight in the percentage rangediscussed above are preferred. A specific example would be such a polyolhaving an average molecular weight of about 8000 wherein the ethyleneoxygroups account for 7.5%-12% by weight of the total molecular weight.Such polyols can be prepared by reacting an alkylene diamine such asethylene diamine, propylene diamine, hexamethylene diamine etc., withpropylene oxide until the desired weight of the hydrophobic portion isreached. Then the resulting product is reacted with ethylene oxide toadd the desired number of hydrophilic units to the molecules.

Another commercially available polyoxyalkylene polyol demulsifierfalling within this preferred group is Dow Polyglycol 112-2, a triolhaving an average molecular weight of about 4000-5000 prepared frompropylene oxides and ethylene oxides, the ethyleneoxy groups comprisingabout 18% by weight of the triol. Such triols can be prepared by firstreacting glyccerol, TME, TMP, etc., with propylene oxide to form ahydrophobic base and reacting that base with ethylene oxide to addhydrophilic portions.

Alcohols useful in this invention also include alkylene glycols andpolyoxyalkylene alcohols such as polyoxyethylene alcohols,polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. Thesepolyoxyalkylene alcohols (sometimes called polyglycols) can contain upto about 150 oxyalkylene groups and the alkylene radical contains from 2to about 8 carbon atoms. Such polyoxyalkylene alcohols are generallydihydric alcohols. That is, each end of the molecule terminates with a--OH group. In order for such polyoxyalkylene alcohols to be useful,there must be at least one such --OH group. However, the remaining --OHgroup can be esterified with a monobasic, aliphatic or aromaticcarboxylic acid of up to about 20 carbon atoms such as acetic acid,propionic acid, oleic acid, stearic acid, benzoic acid, and the like.The monoethers of these alkylene glycols and polyoxyalkylene glycols arealso useful. These include the monoaryl ethers, monoalkyl ethers, andmonoaralkyl ethers of these alkylene glycols and polyoxyalkyleneglycols. This group of alcohols can be represented by the generalformula

    HO--R.sub.A O).sub.P R.sub.B --OR.sub.C

where R_(A) and R_(B) are independently alkylene radicals of 2 to 8carbon atoms; and R_(C) is aryl such as phenyl, lower alkoxy phenyl, orlower alkyl phenyl; lower alkyl such as ethyl, propyl, tertbutyl,pentyl, etc.; and aralkyl such as benzyl, phenylethyl, phenyllpropyl,p-ethylphenylethyl, etc.; p is zero to about eight, preferably two tofour. Polyoxyalkylene glycols where the alkylene groups are ethylene orpropylene and p is at least two as well as the monoethers thereof asdescribed above are very useful.

The monohydric and polyhydric alcohols useful in this invention includemonohydroxy and polyhydroxy aromatic compounds. Monohydric andpolyhydric phenols and naphthols are preferred hydroxyaromaticcompounds. These hydroxy-substituted aromatic compounds may containother substituents in addition to the hydroxy substituents such as halo,alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, thehydroxy aromatic compound will contain 1 to 4 hydroxy groups. Thearomatic hydroxy compounds are illustrated by the following specificexamples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol,alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol,eugenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol,phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol,2,4-dibutylphenol, propenetetramer-substituted phenol, di-dodecylphenol,4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol,polyisobutenyl-(molecular weight of about 1000)-substituted phenol, thecondensation product of heptylphenol with 0.5 moles of formaldehyde, thecondensation product of octylphenol with acetone,di(hydroxyphenyl)oxide, di(hydroxyphenyl)sulfide,di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol. Phenol itself andaliphatic hydocarbon-substituted phenols, e.g., alkylated phenols havingup to 3 aliphatic hydrocarbon substituents are especially preferred.Each of the aliphatic hydrocarbon substituents may contain 100 or morecarbon atoms but usually will have from 1 to 20 carbon atoms. Alkyl andalkenyl groups are the preferred aliphatic hydrocarbon substitutents.

Further specific examples of monohydric alcohols which can be usedinclude monohydric alcohols such as methanol, ethanol, isooctanol,dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol,hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol,beta-phenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol,nitro-octadecanol, and dioleate of glycerol. Alcohols useful in thisinvention may be unsaturated alcohols such as allyl alcohol, cinnamylalcohol, 1-cyclohexene-3-ol and oleyl alcohol.

Other specific alcohols useful in this invention are the ether alcoholsand amino alcohols including, for example, the oxyalkylene, oxyarylene-,amino-alkylene-, and amino-arylene-substituted alcohols having one ormore oxyalkylene, aminoalkylene or amino-aryleneoxy-arylene radicals.They are exemplified by Cellosolve, carbitol, phenoxyethanol,heptylphenyl-(oxypropylene)₆ -OH, octyl-(oxyethylene)₃₀ -OH,phenyl-(oxyoctylene)₂ -OH, mono-(heptylphenyloxypropylene)-substitutedglycerol, poly-(styreneoxide), aminoethanol, 3-amino-ethylpentanol,di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylenediamine,N,N,N',N'-tetrahydroxy-trimethylenediamine, and the like.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxyradicals. They are illustrated, for example, by the alkylene glycols andpolyoxyalkylene glycols mentioned above such as ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol, andother alkylene glycols and polyoxyalkylene glycols in which the alkyleneradicals contain 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used. Thecarbohydrates may be exemplified by glucose, fructose, sucrose, rhamose,mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not allof which have been esterified with an aliphatic monocarboxylic acidhaving from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful. Further specific examples of such partially esterifiedpolyhydric alcohols are the monooleate of sorbitol, distearate ofsorbitol, monooleate of glycerol, monostearate of glycerol,di-dodecanoate of erythritol, and the like.

A preferred class of alcohols suitable for use in this invention arethose polyhydric alcohols containing up to about 12 carbon atoms, andespecially those containing three to ten carbon atoms. This class ofalcohols includes glycerol, erythritol, pentaerythritol,dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose,1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis-(hydroxy-methyl)cyclohexanol, 1,10-decanediol,digitalose, and the like. Aliphatic alcohols containing at least threehydroxyl groups and up to ten carbon atoms are particularly preferred.

Another preferred class of polyhydric alcohols for use in this inventionare the polyhydric alkanols containing three to ten carbon atoms andparticularly, those containing three to six carbon atoms and having atleast three hydroxyl groups. Such alcohols are exemplified by glycerol,erythritol, pentaerythritol, mannitol, sorbitol,2-hydroxymethyl-2-methyl-1,3-propanediol(trimethylolethane),2-hydoxymethyl-2-ethyl-1,3-propanediol(trimethylopropane),1,2,4-hexanetriol, and the like.

The amines useful in accordance with the present invention may containalcoholic hydroxy substituents and alcohols that are useful can containprimary, secondary, or tertiary amino substituents. Thus, hydroxyaminescan be catagorized as both amine and alcohol provided they contain atleast one primary or secondary amino group. If only tertiary aminogroups are present, the amino alcohol belongs only in the alcoholcatagory. Typically, the hydroxyamines are primary, secondary ortertiary alkanol amines or mixtures thereof. Such amines can berepresented, respectfully, by the formulae: ##STR20## wherein each R isindependently a hydrocarbyl group of one to about eight carbon atoms orhydroxyl-substituted hydrocarbyl group of two to about eight carbonatoms and R' is a divalent hydrocarbyl group of about two to about 18carbon atoms. The group --R'--OH in such formulae represents thehydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclicor aromatic group. Typically, it is an acyclic straight or branchedalkylene group such as an ethylene, 1,2-propylene, 1,2-butylene,1,2-octadecylene, etc. group. Where two R groups are present in the samemolecule they can be joined by a direct carbon-to-carbon bond or througha heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or8-membered ring structure. Examples of such heterocyclic amines includeN-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines,-oxazolidines, -thiazolidines and the like. Typically, however, each Ris a lower alkyl group of up to 7 carbon atoms.

The hydroxyamines can also be ether N-(hydroxyl-substitutedhydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described hydroxy amines (these analogs alsoinclude hydroxyl-substituted oxyalkylene analogs). SuchN-(hydroxyl-substituted hydrocarbyl) amines can be conveniently preparedby reaction of epoxides with afore-described amines and can berepresented by the formulae: ##STR21## wherein x is a number from 2 toabout 15 and R and R' are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also beused in accordance with the present invention. Such polyamines can bemade by reacting alkylene amines (e.g., ethylenediamine) with one ormore alkylene oxides (e.g., ethylene oxide, octadecene oxide) of two toabout 20 carbons. Similar alkylene oxide-alkanol amine reaction productscan also be used such as the products made by reacting theafore-described primary, secondary or tertiary alkanol amines withethylene, propylene or higher epoxides in a 1:1 or 1:2 molar ratio.Reactant ratios and temperatures for carrying out such reactions areknown to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl)ethylene diamine, N,N-bis(2-hydroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituteddiethylene triamine, di(hydroxypropyl)-substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higherhomologs obtained by condensation of the above-illustrated hydroxyalkylene polyamines through amino radicals or through hydroxy radicalsare likewise useful. Condensation through amino radicals results in ahigher amine accompanied by removal of ammonia while condensationthrough the hydroxy radicals results in products containing etherlinkages accompanied by removal of water. Mixtures of two or more of anyof the aforedescribed mono- or polyamines are also useful.

Particularly useful examples of N-(hydroxyl-substitutedhydrocarbyl)amines include mono-, di-, and triethanol amine,diethylethanol amine, di-(3-hydroxyl butyl) amine, N-(3-hydroxyl butyl)amine, N-(4-hydroxyl butyl) amine, N,N-di-(2-hydroxyl propyl) amine,N-(2-hydroxyl ethyl) morpholine and its thio analog, N-(2-hydroxylethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, o-, m- andp-aminophenol, N-(hydroxyl ethyl) piperazine, N,N'-di(hydroxyl ethyl)piperazine, and the line. Preferred hydroxy amines are diethanolamineand triethanolamine.

Further amino alcohols are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

    R.sub.a --NH.sub.2

where R_(a) is a monovalent organic radical containing at least onealcoholic hydroxy group, according to this patent, the total number ofcarbon atoms in R_(a) will not exceed about 20. Hydroxyl-substitutedaliphatic primary amines containing a total of up to about 10 carbonatoms are particularly useful. Especially preferred are thepolyhydroxyl-substituted alkanol primary amines wherein there is onlyone amino group present (i.e., a primary amino group) having one alkylsubstituent containing up to 10 carbon atoms and up to 6 hydroxylgroups. These alkanol primary amines correspond to R_(a) --NH₂ whereinR_(a) is a mono-0 or polyhydroxy-substituted alkyl group. It isdesirable that at least one of the hydroxyl groups be a primaryalcoholic hydroxyl group. Trismethylolaminomethane is a particularlypreferable hydroxy-substituted primary amine. Specific examples of thehydroxyl-substituted primary amines include 2-amino-1-butanol,2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-analine,2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N'-(beta-aminoethyl)-piperazine,tris(hydroxymethyl)amino methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)-ethyl amine, glucamine, glusoamine,4-amino-3-hydroxy-3methyl-1-butene (which can be prepared according toprocedures known in the art by reacting isopreneoxide with ammonia),N-3-(aminopropyl)-4-(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxy ethoxyethyl)-ethylenediamine, and the like. For furtherdescription of the hydroxy-substituted primary amines contemplated asbeing useful as amines and/or alcohols, U.S. Pat. No. 3,576,743 isincorporated herein by reference for its disclosure of such amines.

The carboxylic derivative compositions produced by reacting theacylating reagents of this invention with alcohols are esters. Bothacidic esters and neutral esters are contemplated as being within thescope of this invention. Acidic esters are those in which some of thecarboxylic acid functions in the acylating reagents are not esterifiedbut are present as free carboxyl groups. Obviously, acid esters areeasily prepared by using an amount of alcohol insufficient to esterifyall of the carboxyl groups in the acylating reagents of this invention.

The acylating agents of this invention are reacted with the alcoholsaccording to conventional esterification techniques. It normallyinvolves heating the acylating agent of this invention with the alcohol,optionally in the presence of a normally liquid, substantially inert,organic liquid solvent/diuent and/or in the presence of esterificationcatalyst. Temperatures of at least about 100° C. up to the decompositionpoint are used (the decomposition point having been definedhereinbefore). This temperature is usually within the range of about100° C. up to about 300° C. with temperature of about 140° C. to 250° C.often being employed. Usually, at least about one-half equivalent ofalcohol is used for each equivalent of acylating agent. An equivalent ofacylating reagent is the same as discussed above with respect toreaction with amines. An equivalent of alcohol is its molecular weightdivided by the total number of hydroxyl groups present in the molecule.Thus, an equivalent weight of ethanol is its molecular weight while theequivalent weight of ethylene glycol is one-half its molecular weight.The amino-alcohols have equivalent weights equal to the molecular weightdivided by the total number of hydroxy groups and nitrogen atoms presentin each molecule.

Many issued patents disclose procedures for reacting high molecularweight carboxylic acid acylating agents with alcohols to produce acidicesters and neutral esters. These same techniques are applicable topreparing esters from the acylating agents of this invention and thealcohols described above. All that is required is that the acylatingagents of this invention are substituted for the high molecular weightcarboxylic acid acylating reagents discussed in these patents, usuallyon an equivalent weight basis. The following U.S. patents are expresslyincorporated herein by reference for their disclosure of suitablemethods for reacting the acylating reagents of this invention with thealcohols described above: U.S. Pat. Nos. 3,331,776; 3,381,022;3,522,179; 3,542,680; 3,697,429; 3,755,169.

Suitable substantially inert, organic liquid solvents or diluents may beused in the reaction processes of the present invention and include suchrelatively low boiling liquids as hexane, heptane, benzene, toluene,xylene, etc., as well as high boiling materials such as solvent neutraloils, bright stocks, and various types of synthetic and naturallubricating oil base stocks. Factors governing the choice and use ofsuch materials are well known to those of skill in the art. Normallysuch diluents will be used to facilitate heat control, handling,filtration, etc. It is often desirable to select diluents which will becompatible with the other materials, which are to be present in theenvironment where the product is intended to be used.

As used in the specification and appended claims, the term"substantially inert" when used to refer to solvents, diluents, and thelike, is intended to mean that the solvent, diluent, etc., is inert tochemical or physical change under the conditions in which it is used soas not to materially interfere in an adverse manner with thepreparation, storage, blending and/or functioning of the compositions,additives, compounds, etc., of this invention in the context of itsintended use. For example, small amounts of a solvent, diluent, etc.,can undergo minimal reaction or degradation without preventing themaking and using of the invention as described herein. In other words,such reaction or degradation, while technically discernible, would notbe sufficient to deter the practical worker of ordinary skill in the artfrom making and using the invention for its intended purposes."Substantially inert" as used herein is, thus, readily understood andappreciated by those of ordinary skill in the art.

As previously described, substantially inert organic liquid solvents ordiluents may be used in this reaction. The compositions of thisinvention can be recovered from such solvent/diluents by such standardprocedures as distillation, evaporation, and the like, when desired.Alternatively, if the solvent/diluent is, for example, a base suitablefor use in a functional fluid, the product can be left in thesolvent/diluent and used to form the lubricating, fuel or functionalfluid composition as described below. The reaction mixture can bepurified by conventional means (e.g., filtration, centrifugation, etc.),if desired.

The aforesaid invention is illustrated by the following specificexamples. In these examples, as well as elsewhere in the specificationand appended claims, all percentages and parts are by weight (unlessotherwise stated expressly to the contrary) and the molecular weightsare number average molecular weights (Mn) as determined by gelpermeation chromatography (GPC).

EXAMPLE 1

A mixture of 1000 parts of n-hexane and 190 parts of aluminum chlorideis cooled to a temperature of -5° to -10° C. 6390 parts of a commercialC₁₅₋₁₈ alpha-olefin is added dropwise to the mixture over a period offour to six hours. The mixture is maintained at a temperature of -5° C.for one hour with stirring. 170 parts of an aqueous solution of sodiumhydroxide is added dropwise to the mixture to deactivate the catalyst.The mixture is filtered. The filtrate is stripped to yield the residueas the desired polymer product (n_(inh) =0.060 (1.0 grams/100 m. CCl₄,30° C.)).

EXAMPLE 2

A mixture of 4862 parts of the polymer prepared in Example 1 and 292parts of maleic anhydride is heated to 180° C. At 180° C. to 200° C.,chlorine is bubbled into the mixture over an eight-hour period. Themixture is then blown with nitrogen for one hour at 180° C. The residueis the desired acylating agent.

EXAMPLE 3

A mixture of 4352 parts of the acylating agent prepared in Example 2 and1088 parts of diluent oil are heated to 160° C. 92.2 partsaminopropylmorpholine and 33.0 parts diethylenetetramine are premixedand then added to the reaction mixture dropwise under a thin stream ofnitrogen. The mixture is maintained at 160° to 170° C. for a total oftwo hours including the period provided for amine addition. The mixtureis filtered and the filtrate is the desired product.

EXAMPLE 4

A mixture of 2175 parts methylene chloride and 90 parts aluminumchloride is cooled to 31 5° C. A mixture of 3000 parts of a commercial1-dodecene available from Gulf Oil Company, 31.2 parts t-butyl chlorideand 2175 parts methylene chloride is premixed and added dropwise to themixture of methylene chloride and aluminum chloride over a period offive hours. After the addition is complete, the reaction mixture ismaintained at -5° C. for one hour. 100 parts sodium hydroxide is addedto the reaction mixture dropwise to deactivate the catalyst. Thereaction mixture is filtered and stripped. The residue is the desiredpolymer product (n_(inh) =0.18 (0.5 grams/100 ml. CCl₄, 30° C.)).

EXAMPLE 5

A mixture of 1700 parts of the polymer prepared in Example 4 and 55parts of maleic anhydride is heated to 170° C. At 170° to 190° C.,chlorine is bubbled into the reaction mixture over a period of ninehours. The reaction mixture is then blown with nitrogen for one hour at190° C. The residue is the desired acylating agent.

EXAMPLE 6

A mixture of 975 parts of the acylating agent prepared in Example 5 and1218 parts of diluent oil are heated to 160° C. A mixture of 20.5 partsaminopropylmorpholine and 10.7 parts of pentaethylenehexamine ispremixed and added to the reaction mixture over a period of 30 minutesunder a thin stream of nitrogen. After addition of the amines, thereaction mixture is heated at 160° C. for one hour under a thin streamof nitrogen. The reaction mixture is filtered. The filtrate is thedesired product.

EXAMPLE 7

At 120° C., 268 parts of di-t-butyl peroxide is added slowly to 5357parts of a commercially available C₁₅₋₁₈ alpha-olefin. The reactionmixture is maintained at 130° C. for 24 hours. The reaction mixture isthen stripped at 205° C. under vacuum to yield the desired polymer(n_(inh) =0.085).

EXAMPLE 8

The procedure of Example 2 is repeated except that the polymer ofExample 1 is replaced on an equal weight basis by the polymer preparedin Example 7.

EXAMPLE 9

The procedure of Example 3 is repeated except that the acylating agentprepared in Example 2 is replaced on an equivalent basis by theacylating agent prepared in Example 8.

As previously indicated, the compositions of this invention are areuseful as additives for lubricants, in which they function primarily asdetergent/dispersants. They can be employed in a variety of lubricantsbased on diverse oils of lubricating viscosity, including natural andsynthetic lubricating oils and mixtures thereof. These lubricantsinclude crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, including automobileand truck engines, two-cycle engines, aviation piston engines, marineand railroad diesel engines, and the like. They can also be used in gasengines, stationary power engines and turbines and the like. Automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulic fluids and other lubricating oil andgrease compositions can also benefit from the incorporation therein ofthe compositions of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral lubricatingoils of the paraffinic, naphthenic, or mixed paraffin-naphthenic types.Oils of lubricating viscosity derived from coal or shale are also usefulbase oils. Synthetic lubricating oils include hydrocarbon oils andhalo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkyl benezenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenols (e.g.,biphenyls, terphenyls, etc.); and the like. Alkylene oxide polymers andinterpolymers and derivatives thereof where the terminal hydroxyl groupshave been modified by esterification, etherification, etc., constituteanother class of known synthetic lubricating oils. These are exemplifiedby the oils prepared through polymerization of ethylene oxide orpropylene oxide, the alkyl and aryl ethers of these polyoxyalkylenepolymers (e.g., methylpolyisopropylene gycol ether having an averagemolecular weight of 1000, diphenyl ether of polyethylene glycol having amolecular weight of 500-1000, diethyl ether of polypropylene glycolhaving a molecular weight of 1000-1500, etc.) or mono- andpolycarboxylic esters thereof, for example, the acetic acid esters,mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo acid diester oftetraethylene glycol. Another suitable class of synthetic lubricatingoils comprises the esters of dicarboxylic acids (e.g., phthalic acid,succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety ofalcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,2-ethylhexyl alcohol, pentaerythritol, etc.). Specific examples of theseesters include dibutyl adipate, di(2-ethylhexyl)-sebacate, di-n-hexylfumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the2-ethylhexyl diester of linoleic acid dimer, the complex ester formed byreacting one mole of sebacic acid with two moles of tetraethylene glycoland two moles of 2-ethyl-hexanoic acid, and the like. Silicon-based oilssuch as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxaneoils and silicate oils comprise another useful class of syntheticlubricants (e.g., tetraethyl-silicate, tetraisopropyl-silicate,tetra-(2-ethylhexyl)-silicate, tetra-(4-methyl-2-tetraethyl)-silicate,tetra-(p-tert-butylphenyl)-silicate,hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)-siloxanes,poly-(methylphenyl)-siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acid (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc., polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type disclosed hereinabove can be used in the lubricantcompositions of the present invention. Unrefined oils are these obtaineddirectly from a natural or synthetic source without further purificationtreatement. For example, a shale oil obtained directly from retortingoperations, a petroleum oil obtained directly from distillation or esteroil obtained directly from an esterification process and used withoutfurther treatment would be an unrefined oil. Refined oils are similar tothe unrefined oils excepted that they have been further treated in oneor more purification steps to improve one or more properties. Many suchpurification techniques are known to those of skill in the art such assolvent extraction, acid or base extraction, filtration, percolation,etc. Rerefined oils are obtained by processes similar to those used toobtain refined oils applied to refined oils which have been already usedin service. Such rerefined oils are also known as reclaimed orreprocessed oils and often are additionally processed by techniquesdirected to removal of spent additives and oil breakdown products.

Generally, the lubricants of the present invention contain an amount ofthe composition of this invention sufficient to provide it withdetergent/dispersant properties. Normally this amount will be about0.05% to about 20%, preferably about 0.1% to about 10% of the totalweight of the lubricant. In lubricating oils operated under extremelyadverse conditions, such as lubricating oils for marine diesel engines,the reaction products of this invention may be present in amounts of upto about 30% by weight.

The invention also contemplates the use of other additives incombination with the nitrogen-containing esters of this invention. Suchadditives include, for example, auxiliary detergents and dispersants ofthe ash-producing or ashless type, corrosion- and oxidation-inhibitingagents, viscosity improving agents, extreme pressure agents, colorstabilizers and anti-foam agents.

The ash-producing detergents are exemplified by oil-soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage such as those prepared by thetreatment of an olefin polymer (e.g., polyisobutene having a molecularweight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontiumand barium.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The commonly employed methods for preparing the basic saltsinvolve heating a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide,carbonate, bicarbonate, or sulfide at a temperature above 50° C. andfiltering the resulting mass. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metallikewise is known. Examples of compounds useful as the promoter includephenolic substances such as phenol, naphthol, alkylphenol, thiophenol,sulfurized alkylphenol, and condensation products of formaldehyde with aphenolic substance; alcohols such as methanol, 2-propanol, octylalcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, andcyclohexyl alcohol; and amines such as aniline, phenylenediamine,phenothiazine, phenyl-beta-naphthylamine, and dodecylamine. Aparticularly effective method for preparing the basic salts comprisesmixing an acid with an excess of a basic alkaline earth metalneutralizing agent and at least one alcohol promoter, and carbonatingthe mixture at an elevated temperature such as 60°- 200 ° C.

Auxiliary ashless detergents and dispersants are so called despite thefact that, depending on its constitution, the dispersant may uponcombustion yield a non-volatile material such as boric oxide orphosphorus pentoxide; however, it does not ordinarily contain metal andtherefore does not yield a metal-containing ash on combustion. Manytypes are known in the art, and any of them are suitable for use in thelubricants of this invention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen-containing compounds such as amine, organic hydroxycompounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these "carboxylic dispersants" are described inBritish Pat. No. 1,306,529 and in many U.S. patents including thefollowing: U.S. Pat. Nos. 3,163,603; 3,351,552; 3,541,012; 3,184,474;3,381,022; 3,542,678; 3,215,707; 3,399,141; 3,542,680; 3,219,666;3,415,750; 3,567,637; 3,271,310; 3,433,744; 3,574,101; 3,272,746;3,444,170; 3,576,743; 3,281,357; 3,448,048; 3,630,904; 3,306,908;3,448,049; 3,632,510; 3,311,558; 3,451,933; 3,632,511; 3,316,177;3,454,607; 3,697,428; 3,340,281; 3,467,668; 3,725,441; 3,341,542;3,501,405; Re 26,433; 3,346,493; 3,522,179.

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably polyalkylene polyamines. Thesemay be characterized as "amine dispersants" and examples thereof aredescribed for example, in the following U.S. Pat. Nos.: 3,275,554;3,454,555; 3,438,757; 3,565,804.

(3) Reaction products of alkyl phenols in which the alkyl group containsat least about 30 carbon atoms with aldehydes (especially formaldehyde)and amines (especially polyalkylene polyamines), which may becharacterized as "Mannich dispersants". The materials described in thefollowing U.S. patents are illustrative: U.S. Pat. Nos. 3,413,347;3,725,480; 3,697,574; 3,726,882; 3,725,277.

(4) Products obtained by post-treating the caboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. Pat. Nos.: 3,036,003; 3,282,955; 3,493,520; 3,639,242;3,087,936; 3,312,619; 3,502,677; 3,649,229; 3,200,107; 3,366,569;3,513,093; 3,649,659; 3,216,936; 3,367,943; 3,533,945; 3,658,836;3,254,025; 3,373,111; 3,539,633; 3,697,574; 3,256,185; 3,403,102;3,573,010; 3,702,757; 3,278,550; 3,442,808; 3,579,450; 3,703,536;3,280,234; 3,455,831; 3,591,598; 3,704,308; 3,281,428; 3,455,832;3,600,372; 3,708,522.

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may becharacterized as "polymeric dispersants" and examples thereof aredisclosed in the following U.S. Pat. Nos.: 3,329,658; 3,666,730;3,449,250; 3,687,849; 3,519,565; 3,702,300.

The above-noted patents are incorporated by reference herein for theirdisclosures of ashless dispersants.

Extreme pressure agents and corrosion- and oxidation-inhibiting agentsare exemplified by chlorinated aliphatic hydrocarbons such aschlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate; phosphorus esters including principally dihydrocarbon andtrihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

The normally liquid fuel compositions of this invention are generallyderived from petroleum sources, e.g., normally liquid petroleumdistillate fuels, though they may include those produced syntheticallyby the Fischer-Tropsch and related processes, the processing of organicwaste material or the processing of coal, lignite or shale rock. Suchfuel composition have varying boiling ranges, viscosities, cloud andpour points, etc., according to their end use as is well known to thoseof skill in the art. Among such fuels are those commonly known as motorgasoline, diesel fuels, kerosene, distillate fuels, heating oils,residual fuels, bunker fuels, etc. The properties of such fuels are wellknown to skilled artisans as illustrated, for example, by ASTMSpecifications D #396-73 (Fuel Oils) and D #439-73 (Gasolines) availablefrom the American Society for Testing Materials, 1916 Race Street,Philadelphia, Pa. 19103. Particularly preferred is gasoline, that is, amixture of hydrocarbons having an ASTM boiling point of about 60° C. atthe 10% distillation point to about 205° C. at the 90% distillationpoint. Such gasolines are further described in ASTM SpecificationD-439-68T.

The fuel compositions of the present invention can contain about 0.001%to about 5% (based on the weight of the final composition), preferablyabout 0.001% to about 1%, of the compositions described by thisinvention. The presence of these products can impart many desirablecharacteristics to the fuel composition depending upon the particularcomposition and fuel mixture selected. Thus in gasolines they mayimprove the overall composition ability to retard corrosion of metalparts with which it may come in contact or improve the fuel's ability toclean carburetors and reduce carburetor icing. On the other hand, theseproducts can be used in fuel oil compositions and other normally liquidpetroleum distillate fuel compositions to impart anti-screen cloggingand demulsifying properties to the fuel.

The fuel compositions of this invention can contain, in addition to theproducts of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes, depositpreventers or modifiers such as triaryl phosphates, dyes, cetaneimprovers, anti-oxidants such as 2,6di-tertiary-butyl-4-methylphenol,rust inhibitors, such as alkylated succinic acids and anhydrides,bacteriostatic agents, gum inhibitors, metal deactivators, uppercylinder lubricants and the like.

In one embodiment of the present invention, the afore-describedcompositions are combined with other ashless dispersants for use infuels and lubricants. Such ashless dispersants are preferably esters ofa mono- or polyol and a high molecular weight mono- or polycarboxylicacid acylating agent containing at least 30 carbon atoms in the acylmoiety. Such esters are well known to those of skill in the art. See,for example, French Pat. No. 1,396,645; British Pat. Nos. 981,850 and1,055,337; and U.S. Pat. Nos. 3,255,108; 3,311,558; 3,331,776;3,346,354; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428;3,708,522; and British Patent Specification No. 1,306,529. These patentsare expressly incorporated herein by reference for their disclosure ofsuitable esters and methods for their preparation.

Generally, the weight ratio of the compositions of this invention to theaforesaid ashless dispersants is about 0.1 to 10.0, preferably about 1.0to 10 parts of reaction product to one part ashless dispersant.Preferred weight ratios are between 0.5 to 2.0 parts reaction product to1 part dispersant. In still another embodiment of this invention, theinventive additives are combined with Mannich condensation productsformed from substituted phenols, aldehydes, polyamines, and substitutedpyridines. Such condensation products are described in U.S. Pat. Nos3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277, which areincorporated herein by reference for their disclosure of the preparationof the Mannich condensation products and their use in fuels andlubricants. When the additives of this invention are combined with theMannich condensation products, a weight ratio of about 10 to about 0.1parts reaction product of this invention per one part Mannichcondensation product is used.

The compositions of this invention can be added directly to the fuel orlubricant. Preferably, however, they are diluted with a substantiallyinert, normally liquid organic diluent such as mineral oil, naphtha,benzene, toluene or xylene, to form an additive concentrate. Theseconcentrates usually contain about 20-90% by weight of the compositionof this invention and may contain, in addition, one or more otheradditives known in the art or described hereinabove.

This invention relates to improved lubricating oils and normally liquidfuels and particularly concerns automobile and diesel crankcaselubricating oils containing the above-described novel compositions.

An engine performance levels increase, there is a need for moreadditives and higher treatment levels of additives in lubricating oils.But, the lubricants must continue to provide resistance to thickening atlow temperatures and thinning at high temperatures.

The formulation of lubricant compositions containing higher levels(i.e., about 2.5% by weight of chemical or higher for automobilecrankcase lubricating oils and 6% by weight of chemical or higher fordiesel crankcase lubricating oils) of prior art detergent/dispersantsbecomes difficult because of the thickening contribution of the priorart detergent/dispersants at low temperatures, particularly at 0° F.

The novel compositions of this invention help alleviate this problem.This invention provides substituted carboxylic acid acylating agents andacylated amine and alcohol derivatives thereof which have lowerviscosities than those of the prior art and, therefore, contribute lessto the low temperature viscosity of a formulation.

Thus, one of ordinary skill in the art of lubricants and fuels would seeother advantages of this invention. These other advantages include suchbenefits as less diluent/solvent needed to facilitate handling, thusreducing costs, storage space, etc. Also, lubricating oils could beformulated using higher viscosity base oils and, therefore, yieldinggreater flexibility in lubricant formulation.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thisspecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

What is claimed is:
 1. A composition comprising: the reaction product of(I):(A) one or more alpha-beta olefinically unsaturated carboxylicreagents containing two to about 20 carbon atoms exclusive of thecarboxyl-based groups with (B) one or more olefin polymers of at least30 carbon atoms selected from the group consisting of(i) polymers of C₁₂-C₃₀ mono-olefins with the proviso that said polymers exclude polymersderived from ethylene and (ii) chlorinated or brominated analogs of(i):reacted with (II) one or more amines, one or more alcohols, or amixture of one or more amines and/or one or more alcohols.
 2. Thecomposition of claim 1 wherein components (A) and (B) are reacted in thepresence of chlorine or bromine.
 3. The composition of claim 1 whereincomponent (A) is monobasic or polybasic.
 4. The composition of claim 1wherein component (A) is carboxylic acid or a functional derivative ofcarboxylic acid.
 5. The composition of claim 1 wherein component (A) isrepresented by the formula ##STR22## wherein R is hydrogen or asaturated aliphatic or heterocyclic group, R₁ is hydrogen or a loweralkyl group and the total number of carbon atoms in R and R₁ does notexceed 18 carbon atoms.
 6. The composition of claim 1 wherein component(A) is a dibasic carboxylic acid or a derivative of such dibasiccarboxylic acid.
 7. The composition of claim 1 wherein component (A) isa mono-, di-, tri- or tetracarboxylic acid, or a derivative of such acidselected from the group consisting of anhydride, ester, acylatednitrogen, acid halide, nitrile, ammonium salt and metal salts.
 8. Thecomposition of claim 1 wherein component (A) is selected from the groupconsisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid,lower alkyl esters of such acids, maleic anhydride, and mixtures of twoor more of any of these.
 9. The composition of claim 1 wherein component(A) is maleic anhydride.
 10. The composition of claim 1 wherein saidolefin polymers (B) are homopolymers and/or interpolymers ofmono-olefins of from 12 to 30 carbon atoms.
 11. The composition of claim1 wherein said olefin polymers (B) are homopolymers and/or interpolymersof mono-olefins of from 18 to 24 carbon atoms.
 12. The composition ofclaim 1 wherein said olefin polymers (B) are homopolymers and/orinterpolymers of mono-olefins of from 15 to 18 carbon atoms.
 13. Thecomposition of claim 1 wherein said olefin polymers (B) are polymers ofmono-1-olefins of from 12 to 30 carbon atoms.
 14. The composition ofclaim 1 wherein said olefin polymers (B) are polymers of mono-1-olefinsof from 15 to 18 carbon atoms.
 15. The composition of claim 1 whereinsaid olefin polymers (B) are polymers of mono-1-olefins of from 18 to 24carbon atoms.
 16. The composition of claim 1 wherein said olefinpolymers (B) are polymers of mono-olefins selected from the groupconsisting of the following alpha-olefin mixtures: C₁₅₋₁₈ alpha-olefins;C₁₂₋₁₆ alpha-olefins; C₁₄₋₁₆ alpha-olefins; C₁₄₋₁₈ alpha-olefins; C₁₆₋₁₈alpha-olefins; C₁₆₋₂₀ alpha-olefins; and C₂₂₋₂₈ alpha-olefins.
 17. Thecomposition of claim 1 wherein component (B) has an average of about 30to 3500 carbon atoms.
 18. The composition of claim 1 wherein component(B) has an average of about 50 to about 700 carbon atoms.
 19. Thecomposition of claim 1 wherein component (B) has a number averagemolecular weight in the range of about 420 to about 50,000.
 20. Thecomposition of claim 1 wherein component (B) has a weight averagemolecular weight in the range of about 420 to about 100,000.
 21. Thecomposition of claim 1 wherein component (B) has an inherent viscosityin the range of about 0.03 to about 1.5 deciliters per gram.
 22. Thecomposition of claim 1 wherein component (II) is a monoamine or apolyamine.
 23. The composition of claim 1 wherein component (II)comprises at least one amine characterized by the presence within itsstructure of at least one H--N<group.
 24. The composition of claim 1wherein component (II) is hydrazine or a substituted hydrazine.
 25. Thecomposition of claim 1 wherein component (II) has at least one primaryamino group.
 26. The composition of claim 1 wherein component (II) is apolyamine containing at least two H--N<groups.
 27. The composition ofclaim 1 wherein component (II) is a polyamine amine group containing atleast two H--N21 groups, either or both of which are primary orsecondary amines.
 28. The composition of claim 1 wherein component (II)is a monohydric or polyhydric alcohol.
 29. The composition of claim 1wherein component (II) is an aliphatic monoamine of up to 40 carbonatoms.
 30. The composition of claim 1 wherein component (II) is acycloaliphatic monoamine.
 31. The composition of claim 1 whereincomponent (II) is an aromatic monoamine.
 32. The composition of claim 1wherein component (II) is an aliphatic, cycloaliphatic or aromaticpolyamine.
 33. The composition of claim 1 wherein component(II) is ahydroxyamine.
 34. The composition of claim 1 wherein component (II) isan aminosulfonic acid.
 35. The composition of claim 1 whereincomponent(II) is a hydrocarbyl mono- or polyamine prepared by reacting achlorinated polyolefin having a molecular weight of at least 400 withammonia or amine.
 36. The composition of claim 1 wherein component (II)is a branched polyalkylene polyamine.
 37. The composition of claim 1wherein component (II) is polyoxyalkylene diamine or polyoxyalkylenetriamine, said diamine and said triamine having an average molecularweight in the range of about 200 to about
 4000. 38. The composition ofclaim 1 wherein component (II) is an alkylene polyamine of the formula##STR23## wherein n is a number from 1 to 10, each R" is independently ahydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbylgroup having up to 30 carbon atoms, and the Alkylene group has from 1 to10 carbon atoms.
 39. The composition of claim 1 wherein component (II)is ethylene polyamine.
 40. The composition of claim 1 wherein component(II) is a hydroxyalkyl alkylene polyamine having one or morehydroxyalkyl substituents on the nitrogen atoms.
 41. The composition ofclaim 1 wherein component (II) is represented by the formula

    R.sub.1 --(OH).sub.m

wherein R₁ is monovalent or polyvalent organic radical joined to the--OH groups through carbon-to-oxygen bonds and m is an integer of from 1to
 10. 42. The composition of claim 1 wherein component (II) is apolyoxyalkylene alcohol wherein a hydroxy substituted compound, which isrepresented by the formula

    R.sub.2 --(OH).sub.q                                       ( 1)

wherein q is an integer of from 1 to 6 and R₂ is the residue of a mono-or polyhydric alcohol or mono- or polyhydroxy phenol or naphthol, isreacted with an alkylene oxide, which is represented by the formula##STR24## wherein R₃ is an alkyl group of up to four carbon atoms and R₄is hydrogen or an alkyl group of up to four carbon atoms with theproviso that the alkylene oxide (2) does not contain in excess of tencarbon atoms, to form a hydrophobic base, said hydrophobic base thenbeing reacted with ethylene oxide to provide said polyoxyalkylenealcohol.
 43. The composition of claim 1 wherein component (II) is apolyoxyalkylene alcohol of up to about 150 oxyalkylene groups, thealkylene radical containing from 2 to 8 carbon atoms.
 44. Thecomposition of claim 1 wherein component (II) is represented by theformula

    HO--R.sub.A O.sub.P R.sub.B --OR.sub.C

wherein R_(A) and R_(B) are independently alkylene radicals of 2 to 8carbon atoms, R_(C) is aryl, lower alkyl or arylalkyl, and p is zero toeight.
 45. The composition of claim 1 wherein component (II) is amonohydroxy aromatic compound or a polyhydroxy aromatic compound. 46.The composition of claim 1 wherein component (II) is ahydroxy-substituted primary amine of the formula

    R.sub.a --NH.sub.2

wherein R_(a) is a monovalent organic radical containing at least onehydroxy group, the total number of carbon atoms in R_(a) not exceedingabout
 20. 47. The composition of claim 46 wherein the total number ofcarbon atoms in R_(a) does not exceed
 10. 48. The composition of claim46 wherein R_(a) is a mono- or polyhydroxy-substituted alkyl group. 49.The composition of claim 1 wherein component (II) is selected from thegroup consisting of (a) primary, secondary, and tertiary alkanol amineswhich can be represented correspondingly by the formulae: ##STR25## (b)hydroxyl-substituted oxyalkylene analogs of said alkanol aminesrepresented by the formulae: ##STR26## wherein each R is independently ahydrocarbyl group of one to about 8 carbon atoms or hydroxyl-substitutedhydrocarbyl group of 2 to about 8 carbon atoms and R' is a divalenthydrocarbyl group of two to about 18 carbon atoms, and (c) mixtures oftwo or more thereof.